The titanium plate is used as the cathode, the graphene is the anode, and the NaCl is the supporting electrolyte and the oxidation source for the indirect electrooxidation of the starch. The L9(34) orthogonal experiment was carried out with four factors: current density, SS mass fraction, NaCl mass fraction and electrolysis time. The results of orthogonal experiments show that the optimal SS and NaCl mass fractions are 10% and 2%, respectively. The single-current step method was used to investigate the current density and electrolysis time. The results show that the optimal current density is 20 mA/cm2. According to the transition characteristics of the potential in the image, the aldehyde group analysis of the starch oxidation process was carried out, and the optimal time of the dynamic equilibrium of the indirect oxidation experimental system was obtained as the turning point of the potential. The analysis found that the mass fraction of aldehyde-containing starch on the turning point was close to the maximum equilibrium. Auxiliary analysis of FT-IR and XRD showed that significant oxidation changes had occurred between the oxidized starch structure at the turning point and the original starch, and the optimum electrolysis time was determined to be 1200 s. Under this condition, the mass fraction of the aldehyde-containing aldehyde group was 0.432%.